Azo dyestuffs.



- Rhine, and Opladen,

TED STATES PATENT OFFICE- OSKAR G'fi'NTHER, OF LEVERKUSEN, NEAR TO SYNTHETIC PATENTS CO.,- INC., 01"

OPLADEN, GERMAN Y, ASSIG-NORS COLOGNE, AND ARTHUR ZART, OF

NEW YORK, N. Y., A CORPORATION NEW YORK.

.AZO DYESTUFIES.

No Drawing.

Specification of Letters. Patent. Application filed November 7, 1913. Serial N 0. 799,717.

Patented June 30, 1.914.

To all whom it may concern:

Be it known that we, OSKAR GiiN'rHnR and ARTHUR ZART doctors of philosophy, chemists, citizens of the German Empire, residingat Leverkusen, near Cologne-on-the Germany, have invented new and useful Improvements in New Azo Dyestuffs, of which the following is a specification.

It has been found that valuable dyestufi's capable of being further developed can be obtained by diazotizing the dyestuffs obtainable by coupling any diazoor diazoazo compounds with 1.5-aminonaphthol or its sulfonic acids in such a way that the diazo compound enters into the nucleus of the naphthalene ring which contains the amino group and by combining the resulting diazo compounds With such derivatives of the 2.amin0'-5naphthol-7sulfonio acid or its derivatives substituted in l-position as contain diazotizable amino groups in the heteronuclear side chain. Such derivatives of the 2.5.7-aminonaphthol .sulfonic acid are e. g. the aminobenzoyl-2.5-aminonaphth0l-7-sulfonic acid, aminobenzoyl-2.5-aminonaphthol- 1.7-disulfonic acid, the aminophenyl-L2- naphthothiazole-5-oXy-7-sulfonic acid, the aminophenyl 1.2 -naphthimidazole- 5-oXy-7- sulfonic acid, the aminobenzoyl-aminobenzoyl-2-amino-5-naphthol-7-sulfonic acid.

The new products are after being dried and pulverized in the shape of their alkaline salts dark powders soluble in water. Upon reduction with stannous chlorid and hydro- SO;Na-

thol-7-sulfonic acid and Q-para-aminobem zo lamino-6-amino-5-naphthol-7-sulfonisc acid. It dyes cotton agreenish blue-black which after diazotation and on development with methylphenylpyrazolone changes into chloric acid they are broken up into an aromatic amino compound, a 1.4-diamino-5- naphthol compound and a derivative of 2.6- diamino-5-naphthol-7-sulfonic acid containing a diazotizable amino group in the heteronuclear side chain. They dye cotton in dull blue to greenish-black shades, which can be converted (a property which could not have been foreseen) by development with diazotized nitranilin or by diazotation on the fiber and after treatment with suitable developers, such as phenylmethylpyrazolone, aceto-acetic-anilid, etc., into green shades fast to washing and of such purity and fastness to light as could hitherto not have been obtained.

In order to illustrate the new process more fully the following example is given, the parts being by weight :The diazo compound obtained from 223 parts of .Z-naphthylamin-5-sulfonic acid is. combined with 303 parts of the sodium salt of the l-amlno- 5-naphthol-7-sulfonic acid acetylized in the hydroxy group. The resulting intermediate compound is further diazotized by means of 69 parts of N aNO, and added to a solution of 380 parts of 4-aminobenzoyl-2-amino-5- naphthol-7-sulfonic acid (sodium salt) after a further addition of sodium carbonate (if necessary) the acetyl group. is-removed by boiling the mixture and the dye is salted out. It is after being dried and pulverized in the shape of its sodium salt a dark powder having in a free state most probably the formula:

OH l

a beautiful ye1lowish-green. It can also be developed with diazotized para-nitranilin to a pure green shade.

Instead of the Q-naphthylamin 5-sulfonic acid other diazotizable aromatic amino compounds and aminoazo compounds can be used 0. acid, l-n. hthylamin-l-sulfonic acid, 3- chloro-2-tol i1idin4-sulfonic acid, para-nig. Q-naphthylamin-.8-disuIfonicv zene-disult'onic acid, etc. lnstead of the 1.5- am1no-naphthol-7-sulfon1c acid acidylized inv the hydroxyl group this acid itself. or 1.5-aininonaphthl or the 1.5-amino-naph thol-G-sulfonic acid can be used, care being taken that the coupling takes place in the nucleus containing the amino group. Instead of the aminobenzoyl-2.S-amino-naphthol-i-sulfonic acid generally such hetero nuclear derivatives of the 2.5-an1inonaphthol-7-sulfonic acid and their derivatives substituted in 1-position can be used as contain a diazotizable amino group in the heteronuclear side chain, such as aminophenyl 1.2 naphthiinidazole oXy 7 sultonic acid, aminophenyl-1.Z-naphthothiazole-5-oxy-7-sulfonic acid, aminobenzoylaminobenzoyl-2-amino-5-naphthol-7-sulfonic acid etc.

We claim 1. The new azo dyestuffs which are after being dried and pulverized in the shapeof their alkaline salts dark powders soluble in water, yielding upon reduction with stannous chlorid and hydrochloric acid an aromatic amino compound, a lfl-diamino-finaphthol compound and a derivative of 2.6- diamino-ii naphthol-Tsulfonic acid containing a heteronuclear side chain with a diazotizable amino group; dyeing cotton in dull blue to greenish-black shades which can be converted by development with diazotized para-nitranilin into green pure shades fast to washing and light substantially as described.

' 2. The new azo dyestuffs which are after being dried and pulverizedin the shape of: their alkaline salts dark powders soluble in water, yielding upon reduction with stannous chlorid and hydrochloric acid an aromatic aniinosulionic acid a lfl-diainino-finaphthol compoundoand a derivative of 2.6- diancino-5-naphthol 7 sulfonic acid containing a heteronuclear side chain with a diazotizable amino group; dyeing cotton in dull lue to, greenish-black shades which can be converted bydevelopinent with diazotized para-nitranilin into green pure shades fast to washing and light substantially as described.

3. The new azo dyestuffs which are after being dried and pulverized in the shape of their alkaline salts darlrpowders solublein 'water; yielding upon reduction with-stannc'us chlorid and hydrocl'iloric acid-a naphtthylamin sulfonic ZLClCh a l-diamindfinaphthol compound and derivative of 2.6- diamino 5-naphthol-7-sulfonic acid containing a heteronuclear side chain with a diazotizable amino group; dyeing cotton in dull blue to greenish-black shades which can be converted by development with diazotized para-nitranilin into green pure shades fast to washing and light, substantially as described.

4E. The new azo dyestuffs which are after being dried and pulverized in the shape of their alkaline salts dark powders soluble in water yielding upon reduction with stannous chlorid and hydrochloric acid an arc matic amino compound, a lxl-diaruinoed naphthol sulfonic acid and a derivative of 2.6-diaminc-5 -naphthol-7-sulfonic acid containing a heteronuclear side chain with a diazotizable amino group; dyeing cotton in dull blue to greenish-black shades which can be converted by development with diazotized para-nitranilin into green pure shades tast'to washing and light, substantially as described.

5. The new azo dyestuffs which are after being dried and pulverized in the shape of their alkaline salts dark powders soluble in water, yielding upon reduction with stannous chlorid and hydrochloric acid an arcmatic amino sulfonic acid, a lAl-diamino-d naphthol sulfonic acid and a derivative of 2.6-dianiino h-naphthol-Y-sulfonic acid containing a heteronuclear side chain with a diazotizable amino group; dyeing cotton in dull blue to greenish-black shades which. can be converted by development with diasotized para-nitranilin into nure shades fast to washing and li ht. substan tially as described.

6. T new azo dyestuffs which are after being dried and pulverized in the shape of their alkaline salts darl: powders soluble in water, yielding upon reduction with. stannous chlorid and hydrochloric acid a naphthylainin sulfonic acid 1. lCll2tY?QiXiO-5 naphthol sulfonic acid and derivative of -2.6-diamino-5-naphthol-T-sulionic acid containing a heteronuclear side chain with a diazotizable amino group; dyeing cotton in dull. blue to greenish-black shades which can be converted by development with diaz otized para-nitranilin into green pure shades fast to washin and lia'ht substan- 71' tially as described.

7. The new azo dyestufi' having in the shape of its sodium salt most robably the formula:

In testimony whereof we have hereunto set our hands in the presence of two subscribing witnesses.

OSKAR GUNTHER. n s.]

which is after being dried and pulverized a dark powder soluble in water with a greenish-blue coloration; yielding upon reduction with stannous chlorid and hydrochloric acid 2 naphthylamin 5 sulfonic acid, 1.45- diamino-5-naphthol-7-sulfonic acid and 2-para- ARTHUR ZART. [L s.] aminobenzoylamino- 6 amino- 5 -naphthoi-7- sulfonic acid; dyeing cotton a reenish blue- Witnesses:

black which can be 'develope with diazo- ALBERT NUFER,

tized para-nitranilin into a pure. green HELEN NUFER.

shade, substantially as described.

copies of this patent may be obtained for live cents each, by addressing the Commissioner of Patents.

Washington, D. G." 

